Process for the manufacture of modified clays



United States Patent Ofilice 3,356,429

Patented Oct. 31, 1967 1 i 2 3 356 429 1 by adding to bentonite acomplex produced from trif NUF methyloctadecyl ammonium chloride andtallow fatty PROCESS S F amide, the hydrocarbon chain of said organiccomplex Hiroshi Hasegaway Hyogmken, Eiji Suit),v sakyoku, molecule willnot be situated perpendicularly to the basal Kyoto, and Mitsuji Kondo,Usuigun, Gumma-ken, 5 planebetween the clay structural sheets. It lswell known Japan, assignors to Shiraishi Kogyo Kaisha, Ltd., that mmodified clay obtainable by addlng octadecyl Hyogo-ken, Japan amineacetate alone to bentom'te, the hydrocarbon chain N0 Drawing- Filed 11952, 191,325 of amine is situated vertically to the basal plane, butthis (335515 Priority, lgg g g g a June 1961 is limited to a case wherethe quantity of amine added to bentonite greatly exceeds the baseexchange capacity 4 Chums (CL 269-404) 10 of the clay. The industrialutilization value of amine in The present invention relates to modifiedclay obtainsuch an excessive quanmy is Very poor because It creases theability to produce gel in an organic solvent using the modified clay.According to tests, the results of measuring by X-ray able by adding tomontmorillonite clay such as bentonite, a complex produced from higherfatty amine and a nonionic higher orgamc polar compound f to a processdifiraction the spatial structure of modified clay obtained for themanufacture thereof, more particularly relates by adding octadecyl aminealong and a complex to modified y of W111ch hydrocarbon Chalfl ofmolecules duced from octadecyl amine and stearamide to bentonite of thecomplex extends perpendlcularly to a basal plane fo v io ti are as follOCTADECYL ALHNE PLUS BENTONIIE Quantity of amine added to 100 grs.

bentom'te (milliequiyaleuts) 0 0 7 100 125 150 175 Basal plane (001)SpfiClIlg (A.) 9.8 13. 0 13.4 16 6 17.8 17 s 11 s 30. 6 32.6 31.6Separation of the structural sheets (A.)- 0 3. 2 3. 6 6, 3 0 3. g 3 0 o3 22 g 2L3 State of arrangement of hydrocarbon chain to basal plane (2)2 2 (a) (a) (a) 1 Parallel 1 molecular layer. 2 Parallel 2 molecularlayers. 3 Vertical 1 molecular layer.

COMPLEX OF OCTADEOYL AMINE AND STEARAMIDE (1:1 MOL. RATIO) PLUSBENTONITE Quantity of amine added to 100 grs.

bcntonite (milllequivalents) 0 5 40 50 Basal plane (001) spacings (A.)-9. 8 13. 0 14.0 31.6 31.6 31.6 31.6 31.6 32.6 31.6 Separation of thestructural sheets (A.) 0 3. 2 4.2 21. 8 21. 8 21. 8 21. 8 21. 8 22.821.8 State of arrangement of hydrocarbon chain to basal plane 2 2 2 2 21 Parmel 1 molecular layer. 2 Vertical 1 molecular layer. (001) betweenthe clay structural sheets, and to a proc- It can be known that ahydrocarbon chain is arranged ess for the manufacture thereof.perpendicularly to the basal plane by the fact that the In the reactionbetween montmorillonite and an or- 4 separation of the structural sheetsagrees with the length ganic compound, there is an ionic reactioninvolving of the corresponding hydrocarbon chain. The calculated theso-called base exchange wherein an inorganic cation value of the chainlength of octadecyl radical is 21.25 A. of the clay is substituted by anorganic cation and also In case of amine alone, hydrocarbon chain isdirected a nonionic reaction wherein hydrated water of clay isperpendicularly to the basal plane by addition of amine substituted byan organic polar compound although the 45 of 125 milliequivalents whichis more than the base exreaction is not followed by said base exchange.If the change capacity of bentonite (about 100 milliequivaorganic cationor a nonionic organic polar compound lents/ 100 grs.), but in the caseof a complex, the hydrois made to react with montmorillonite, theseorganic carbon chain can be oriented perpendicularly to the basalmolecules penetrate into and between the montmorillonite plane by theaddition of a quantity of complex of only 50 sheets, and the basal planespacings of montmorillonite 5O milliequivalents. Therefore, the presentinvention relates become wider. The width of these basal plane spacingsto modified clay comprising a chain hydrocarbon radical depends upon thekind of organic compound and the formed of organic complex moleculeswhich is directed quantity of the organic compound added to clay.Genperpendicularly to the basal plane (001) between the clay erallyspeaking, it is widely known that organic molestructural sheets. Themodified clay is produced by adding cules lie between themontmorillonite sheets and extend 55 to montmorillonite clay a complexobtained from 1 mol. parallel to the basal plane. of a higher fattyamine belonging to a class from the pri- The present invention involvesthe manufacture of mary through the tertiary classes and having morethan 1 modified clay wherein the hydrocarbon chain of said chainhydrocarbon radical comprising more than 10 carorganic complex moleculehas been made to extend perbon atoms, and 1 mol of a nonionic higherorganic polar pendicularly to the base plane between the montmoril- 60compound having more than 1 chain hydrocarbon radical lonite sheets byadding to the montmorillonite a comcomprising more than 10 carbon atoms,and also relates plex produced from a higher fatty amine belonging totoa process for the manufacture thereof. classes from the primary to thetertiary (excepting the According to the present invention, if a complexof quaternary ammonium salt) and a nonionic higher orhigher fatty amineand nonionic higher organic polar comganic polar compound. 65 Pound isadded to clay, it is possible to make the hydro- In order to obtain suchmodified clay wherein the carbon chain of the organic complex moleculesextend hydrocarbon chain of the organic complex molecule hasperpendicularly to the basal plane between the clay strucbeen made toextend perpendicularly to the basal plane, tural sheets by adding aquantity of the complex which the quaternary armnomum salt cannot beused instead is somewhat smaller or slightly more than the quantity ofthe higher fatty amine belonging to the primary 70 of amine addedin caseamine alone is added.

through the tertiary classes, which is used in the present The points ofadvantage of the present invention are as invention. For example, in themodified clay obtainable follows:

Firstly, as a result of hydrocarbon chain of organic complex moleculesbeing directed perpendicularly to the basal plane, separation of thestrucurtal sheets of clay is extremely large. Because of this, theforces of adhesion between the clay structural sheets become weak, andconsequently it is extremely easy to crush dry cake. For example, drycake of modified clay obtained by adding 100 milliequivalents/ 100 grs.of the complex of octadecyl amine-stearamide (1:1 mol. ratio) can bepulverized by grinding it with the fingertip, while dry cake ofheretofore known modified clay, for example, modified clay obtained byadding a complex of trimethyloctadecyl ammonium chloride-tallow fattyamide to bentonite forms a fairly hard aggregated lump, and therefore itneeds a much greater grinding force to obtain pulverization of thelumps.

Secondly, in case amine alone is added, the hydrocarbon chain cannotbecome oriented perpendicularly to the basal plane unless amine in aquantity which greatly exceeds the base exchange capacity of the clay isadded. The gel forming properties of modified clay in an organic solventare greatest when the quantity of amine is chemically equivalent to thebase exchange capacity of clay, and if a greater amount of amine isadded, the gel forming properties are impaired. Where modified clayaccording to the present invention is concerned, it is satisfactory toadd a quantity of amine which is less, when a complex is added, than thequantity of amine added in case amine alone is added and because ofthis, impairment of the gel forming properties due to excess amine areavoided.

All types of montmorillonite clays such as bentonite, Japanese acidclay, hectorite, nontronite, etc. can be used as inorganic materials forpracticing the present invention.

As a complex which reacts on the clay and which is capable of producinga hydrocarbon chain extending perpendicularly to the basal plane betweenthe clay structural sheets, there may be used any complex produced bythe combining of any of the higher fatty amines belonging to classesfrom the primary through the tertiary classes such as dodecyl amine,octadecyl amine, methyloctadecyl amine, dioctadecyl amine anddimethyloctadecyl amine; amide such as stearamide and palmitamide;alcohol such as dodecyl alcohol and cetyl alcohol; nitrile such assteamnitrile and palmitonitrile; ester such as methylstearate,ethylpalmitate and polyoxyethylene monostearate; and ether such aspolyoxyethylene lauryl ether and polyoxyethylene stearyl ether with anynonionic higher organic polar compound similar thereto at the mol. ratioof 1:1.

In order to produce a complex used for the purpose of practicing thepresent invention, it is possible either to make a higher fatty aminesalt of a water soluble acid such as acetic acid, hydrochloric acid,sulfuric acid, phosphoric acid and for-mic acid, and then mix said saltof water soluble acid with a nonionic higher organic polar compoundafter melting, or to mix higher fatty amine with a nonionic higherorganic polar compound and then add the aforesaid acid thereto. As theprocess for adding a complex to clay, it suffices to make the complexand a dispersion of the clay in water, separately, and to add thecomplex as an emulsion to'the clay dispersion while the latter isundergoing agitation.

The present invention is illustrated by the following examples.

Example 1 100 grs. of purified bentonite was dispersed in 5 l. of water.On the other hand, a complex was produced by heating and melting 0.1mol. of octadecyl amine acetate and 0.1 mol. of stearamide, and saidcomplex was emulsified by making it disperse in 1 l. of water. Thecomplex emulsion was added to the aqueous bentonite suspension whileagitating the latter. The product was dried and ground after it had beensubjected to suction filtration.

The product was dried by preserving it in a vacuum desiccator for 12hours, and then its spatial structure was measured by using aGeiger-Miiller counter X-ray spectrometer and the results were asfollows:

A. Basal plane (001) spacings 31.6 Separation of the structural sheets21.8

A. Basal plane (001) spacings 20.1 Separation of the structural sheets10.3

This olay comprised a hydrocarbon chain of organic compound moleculesextending parallel to the basal plane.

Example 2 The same operation as that in Example 1 was made by using 0.1mol. of stearonitrile instead of stearamide as in Example 1. The spatialstructure of the modified clay thus obtained was just the same as thestructure of the modified clay obtained by using a complex of octadecylaminestearamide.

Example 3 A. Basal plane (001) spacings 38.0 Separation of thestructural sheets 28.2

The product was a modified clay comprising a hydrocarbon chain oforganic complex molecules extending perpendicularly to the basal plane.Moreover, the separation of the structural sheets was extremely large.This was due to the C H NH molecules contained in the fully hydrogenatedrapeseed fatty amine.

What we claim is:

1. The method for producing a modified montrnorillonite clay in which achain hydrocarbon radical of organic complex molecules extendsperpendicularly to the basal plane (001) between the clay structuralsheets, said method comprising the steps of adding to montmorilloniteclay a complex which is produced by melting and mixing 1 mol. of higherfatty amine together with 1 mol. of a member of the group consisting ofhigher fatty amide and higher fatty nitrile; adding to the mixture with1 mol. of the group consisting of acetic acid and a complex which isproduced by melting and mixing 1 mol. of higher fatty amine acetatetogether with 1 mol. of higher fatty amide or higher fatty nitrile, saidchain having from 12 to 22 carbon atoms.

2. The method according to claim 1, wherein said higher fatty amine isselected from the group consisting of octadecyl amine and completelyhydrogenated rapeseed fatty amine.

3. The method according to claim 1, wherein said higher fatty amide isselected from the group consisting of stearamide and stearonitrile.

4. A process for the manufacture of modified clay in which a dispersionof a complex which is produced by melting and mixing 1 mol. of higherfatty amine together 5 6 With 1 mol. of higher fatty amide or higherfatty nitrile 2,883,357 4/1959 Hardy 260448 and then adding to themixture with 1 mol. of acetic acid, or a complex which is produced bymelting and mixing 1 OTHER REFERENCES mol. of higher fatty amine acetatetogether with 1 mol. of Jordan et Journal of Physlcal and COHOldChemhigher fatty amide or higher fatty nitrile is added with 5 istry,PP- 1196-1208 an aqueous montmorillonite clay dispersion and the productthus obtained is filtrated and dried. CHARLES PARKER 'mary Exammer' A.H. WINKELSTEIN, A. LOUIS MONACELL, References Cited Examinem UNITEDSTATES PATENTS 10 1. R. PELLMAN, R. v. HINES, Assistant Examiners.2,531,427 11/1950 Hauser 260-448

1. THE METHOD FOR PRODUCING A MODIFIED MONTMORILLONITE CLAY IN WHICH ACHAIN HYDROCARBON RADICAL OF ORGANIC COMPLEX MOLECULES EXTENDSPERPENDICULARLY TO THE BASAL PLANE (001) BETWEEN THE CLAY STRUCTURALSHEETS, SAID METHOD COMPRISING THE STEPS OF ADDING TO MONTMORILLONITECLAY A COMPLEX WHICH IS PRODUCED BY MELTING AND MIXING 1 MOL. OF HIGHERFATTY AMINE TOGETHER WITH 1 MOL. OF A MEMBER OF THE GROUP CONSISTING OFHIGHER FATTY AMIDE AND HIGHER FATTY NITRILE; ADDING TO THE MIXTURE WITH1 MOL. OF THE GROUP CONSISTING OF ACETIC ACID AND A COMPLEX WHICH ISPRODUCED BY MELTING AND MIXING 1 MOL. OF HIGHER FATTY AMINE ACETATETOGETHER WITH 1 MOL. OF HIGHER FATTY AMIDE OR HIGHER FATTY NITRILE, SAIDCHAIN HAVING FROM 12 TO 22 CARBON ATOMS.